Connect public, paid and private patent data with Google Patents Public Datasets

Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof

Download PDF

Info

Publication number
US4945125A
US4945125A US07000389 US38987A US4945125A US 4945125 A US4945125 A US 4945125A US 07000389 US07000389 US 07000389 US 38987 A US38987 A US 38987A US 4945125 A US4945125 A US 4945125A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
silicone
ptfe
process
resin
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07000389
Inventor
Joseph A. Dillon
Mark E. Dillon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Donaldson Co Inc
Original Assignee
Tetratec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18Homopolymers or copolymers or tetrafluoroethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/0004Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/0009Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the articles
    • B29C47/0021Flat flexible articles, e.g. sheets, foils or films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2027/00Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene, Gore Tex (R)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/20Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2427/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2483/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/47Processes of splitting film, webs or sheets

Abstract

A process for producing a semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomers is described which comprises the steps of (1) intimately blending a mixture of a major amount of unsintered and unfibrillated particulate polytetrafluoroethylene dispersion resin and minor amounts of (A) a hydrocarbon liquid and (B) an addition curable silicone composition consisting essentially of a polydiorganosiloxane having alkenyl unsaturation, an organohydrogenpoly-siloxane crosslinking agent, a catalyst for promoting crosslinking of said polysiloxane, and an inhibitor for the catalytic reaction; (2) forming said blend into an extrudable shape; (3) biaxially extruding said blend through a die into a shaped extrudate product having a randomly fibrillated structure; (4) evaporating said hydrocarbon liquid, and activating said catalyst so as to generate a cured silicone elastomer and polytetrafluoroethylene semi-interpenetrating polymer network comprising said fibrillated extrudate structure. Products produced by this process have improved physical properties as compared to extruded fibrillated polytetrafluoroethylene dispersion resin alone.

Description

FIELD OF THE INVENTION

The invention relates to novel compositions comprising semi-interpenetrating polymer networks of polytetrafluoroethylene and silicone elastomers, a process for making such compositions, and shaped products formed from such compositions. More particularly, it relates to the compositions produced by (1) intimately blending a mixture of a major amount of unsintered and unfibrillated particulate polytetrafluoroethylene dispersion resin and minor amounts of (A) a hydrocarbon liquid and (B) an addition curable silicone composition consisting essentially of a polydiorganosiloxane having alkenyl unsaturation, an organohydrogenpolysiloxane crosslinking agent, a catalyst for promoting crosslinking of said polysiloxane, and an inhibitor for the catalytic reaction; (2) forming said blend into an extrudable shape; (3) biaxially extruding said blend through a die into a shaped product having a randomly fibrillated structure; (4) evaporating said hydrocarbon liquid, and activating said catalyst so as to generate a cured silicone elastomer and polytetrafluoroethylene semi-interpenetrating polymer network comprising said fibrillated structure.

DESCRIPTION OF THE PRIOR ART

In U.S. Pat. No. 3,315,020, the disclosure of which is incorporated herein by reference, there is disclosed a process for preparing sheet-like articles of biaxially fibrillated polytetrafluoroethylene which, though in the unsintered state, have high elongation and strength in all directions in the major plane of the sheet. In this process, a relatively large cylinder of compacted unfibrillated dispersion grade polytetrafluoroethylene (PTFE) particles is passed through a die having two orifices in series. The first orifice is a round, square or rectangular orifice and the second orifice is a long slit-shaped orifice. This extrusion of particulate PTFE is aided by the pre-blending with the compacted particles of an organic fluid lubricant such as for example kerosene, VM&P naptha and Isobars. The resultant extrusion produces a continuous sheet of biaxially oriented fibrillated structure of PTFE partially saturated with volatile organic liquid. Under certain processing conditions, the hydrocarbon is evaporated before further processing of the PTFE sheet, such as sintering. For the purposes of this invention, biaxial fibrillation refers to the extrusion method disclosed in U.S. Pat. No. 3,315,020. Although unsintered (i.e. not having been heated to above 327° C.), PTFE dispersion grade resin is highly crystalline (approx. 95%) and has a very high melt viscosity, when heated to temperatures above 327° C., some of the PTFE crystallites deform, thereby increasing the amorphous content of the polymer. Such heating and subsequent cooling of the polymer to temperatures below 327° C. produces sintered PTFE. The sintering of shaped unsintered PTFE structures while maintaining the shape produces a thermosetting effect upon the polymer, thus enabling shape retention.

In the process of biaxial fibrillation of dispersion grade PTFE resin, lower extrusion pressures are desirable for economic as well as qualitative reasons. The configurations of the die, the ratio of crossectional preform area to die orifice area (reduction ratio), extrusion speed and the amount of lubricant determine the pressure necessary to force a given PTFE resin through a die. However, the obvious approach of achieving lower pressures by over lubrication is detrimental. The extruded material may become overly oriented in the machine direction and suffer a significant loss in transverse direction strength. Also, when excessive lubricant is evaporated, voids are created without leaving any remaining structure having orientation, thereby causing loss of strength. Perhaps the most significant problem of over lubrication is merely the softness of the extrusion that occurs, thereby severely restricting further processing, such as calendering and stretching.

Calendering of continuous biaxially fibrillated PTFE extrudate is usually accomplished while the extrudate still contains the hydrocarbon lubricant, and involves compression between rolls spaced apart by a predetermined distance and consequent elongation. Normally, the extrudate is then heated to a temperature at which the hydrocarbon lubricant will be safely evaporated in a reasonable period of time. In the manufacture of pipe-thread sealant, further orientation of the extrudate is accomplished by linear stretching using differential speed rollers on the dried material or on material still containing hydrocarbon lubricant. In the production of micro-porous PTFE membranes, linearly oriented extrudate of the biaxial fibrillation process is given further transverse orientation by use of equipment such as tenter frames or the like. The membranes thus produced are normally heated to above 327° C. and subsequently cooled to effect sintering.

In the prior art processes of modifying the characteristics of biaxially fibrillated PTFE extrudate, difficulties arise in attempts to produce uniform extrudate having satisfactory orientation of fibrillated material to facilitate adequate transverse stretching. One reason for this difficulty is the low transverse elongation inherent in linearly oriented material. Examples of these difficulties are found in U.S. Pat. No. 4,187,390.

BRIEF SUMMARY OF THE INVENTION

We have unexpectedly discovered that the prior art process of biaxial fibrillation of PTFE may be modified so as to produce novel products comprising a biaxially fibrillated semi-interpenetrating polymer network of PTFE and cured silicone elastomers having increased strength and uniformity. Such products facilitate the production of stretched and sintered end products having functions comparable to those of microporous PTFE tape and film. The products of this invention have distinctly different properties than the starting materials from which they are formulated.

BRIEF DESCRIPTION OF THE DRAWING

The drawing is a scanning electron microphotograph of a shaped product produced by the process of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The first step in the process of this invention is to intimately blend a mixture of a major amount of unsintered and unfibrillated particulate PTFE dispersion resin and minor amounts of (A) a hydrocarbon liquid and (B) an addition curable silicone composition consisting essentially of a polydiorganosiloxane having alkenyl unsaturation, an organohydrogenpolysiloxane cross linking agent, a catalyst for promoting crosslinking of said polysiloxane, and an inhibitor for the catalytic reaction. The mixture is necessarily blended by means of a liquid-solids blender or by jar tumbling to avoid any substantial shearing of the PTFE dispersion resin.

Suitable unsintered and unfibrillated PTFE dispersion resin is manufactured by E. I. du Pont de Nemours & Co., Inc. under the designations TEFLON® 6 and 6C; and by Imperial Chemical Industries as FLUON®CD1, CD123 and CD525.

Alkenyl-containing polydiorganosiloxanes typically employed in the practice of the present invention can have viscosities up to 100,000,000 centipoise or more at 25° C., for example, in accordance with the teaching of U.S. Pat. No. 4,061,609 to Bobear. It has been found that excellent results are obtained when the viscosity of the alkenyl-containing polysiloxane is from about 500 centipoise to 50,000 centipoise at 25° C., and especially when the viscosity is from about 3000 centipoise to 6000 centipoise at 25° C.

Organohydrogenpolysiloxanes that can be utilized in the present invention may be linear or resinous and have viscosities of between about 25 centipoise and 10,000 centipoise at 25° C., with the preferred range being from about 100 centipoise to about 1000 centipoise at 25° C.

The curing catalyst can be either an organic peroxide or a precious metal containing material. Suitable organic peroxides include dibenzoyl peroxide, bis-2,4-dichlorobenzol peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, and dicumyl peroxide. Precious metal containing catalysts can be based on the metals rhodium, ruthenium, palladium, osmium, irridium and platinum. It is particularly preferred that a platinum metal complex be employed as the catalyst, for example, as taught by Ashby in U.S. Pat. Nos. 3,159,601 and 3,159,662, Lamoreaux in U.S. Pat. No. 3,220,970, Karstedt in U.S. Pat. No. 3,814,730, and Modic in U.S. Pat. No. 3,516,946.

In an especially preferred embodiment, the addition curable silicone composition further includes a reinforcing organopolysiloxane resin of the type disclosed in U.S. Pat. No. 3,284,406 to Nelson or U.S. Pat. No. 3,436,366 to Modic. Briefly, such resins are copolymers of Si02 units, (CH3)3 Si00.5 units and (CH3)2 ═CH)Si00.5 units, and Si02 units, (CH3)3 Si00.5 units and (CH3)(CH2 ═CH)Si0 units, respectively. Particularly preferred organopolysiloxane resins are MDQ resins having vinyl unsaturation on monofunctional siloxane units, difunctional siloxane units, or both. The use of such reinforcing organopolysiloxane resins is especially desirable when the viscosity of the alkenyl containing polydiorganosiloxane is less than about 5000 centipoise at 25° C.

It is also contemplated that there may be included any conventional extending and/or reinforcing fillers. Fumed silica has been found to be particularly effective as a reinforcing filler.

In another particularly preferred embodiment of the present invention, the addition curable silicone composition also contains a silane or polysiloxane which functions both as an inhibitor and as an adhesion promoter. One such composition is described in U.S. Pat. No. 3,759,968 to Berger et al. as a maleate or fumarate function silane or polysiloxane. Compositions effective only as an inhibitor are disclosed in U.S. Pat. No. 4,256,870 to Eckberg and 4,061,609 to Bobear. Other suitable inhibitors will be obvious to those skilled in the art.

It is further contemplated that the silicone can be a condensation curable silicone composition. Generally, condensation curable silicone compositions are available in either one or two packages and comprise (1) a polydiorganosiloxane having terminal hydrolyzable groups, e.g., hydroxyl or alkoxyl, and (2) a catalyst which promotes condensation curing. Such compositions are well known in the art, for example, as described in U.S. Pat. No. 3,888,815 to Bessmer et al.

Alternatively, the polysiloxane network can be prepared by the hydrolytic polycondensation of silanes having the general formula

Y--Si--(OX).sub.3

where each X is independently selected from the group consisting of hydrogen, alkyl radicals, hydroxyalkyl radicals, alkoxyalkyl radicals, and hydroxyalkoxyalkyl radicals, and Y is an alkyl radical, OX, where X is as previously defined, or an amino or substituted amino radical. The use of silanes having hydrolyzable groups to form a polysiloxane network of an inter-penetrating polymer network is discussed in greater detail in U.S. Pat. No. 4,250,074 to Foscante et al.

The hydrocarbon liquid may suitably be a solvent such as VM&P naptha, Isobars and kerosene.

The minor amounts of hydrocarbon liquid and addition curable silicone composition both function in the first step of the process of this invention as a lubricant for the PTFE particles, and therefore care must be used to avoid the known problem of over lubrication. However, when amounts as small as 2% by weight of addition curable silicone composition are incorporated in the blend, extrusion pressures are caused to be lower than in the case of a blend of hydrocarbon liquid and PTFE dispersion resin alone. At the level of 7% by weight incorporation of addition curable silicone composition into the blend, extrusion pressures have been reduced as much as 56%.

In the second step of the process of this invention, the blend is compacted into a preform shape adapted to the configuration necessary for the process of biaxial fibrillation as described in U.S. Pat. No. 3,315,020.

In the third step of the process of this invention, paste extrusion of the preformed blend is carried out in the known manner of biaxial fibrillation as described in U.S. Pat. No. 3,315,020.

In the fourth step of the process of this invention, the hydrocarbon liquid contained in the blend is evaporated, and simultaneously therewith or later the catalyst for the siloxane crosslinking reaction is activated thereby generating a cured silicone elastomer and polytetrafluoroethylene semi-interpenetrating polymer network in the form of the biaxially fibrillated extrudate.

EXAMPLE 1

The following curable silicone composition is prepared.

______________________________________               Parts by Weight______________________________________Vinyl N-stopped polydimethylsiloxane                 68.2(3500 cps at 25° C.)MDQ silicone resin blend                 22.7Dimethyl vinylsiloxane resin blend                  8.2bis (trimethoxysilylpropyl) maleate                  0.9Lamoreaux platinum catalyst                 10 p.p.m.______________________________________

This curable silicone composition was combined with FLUON®CD123 grade polytetrafluoroethylene dispersion resin and VM&P naptha as follows:

Five silicone/VM&P naptha/PTFE dispersion grade resin blends and one VM&P naptha/PTFE blend were prepared using a liquid-solids blender. The resultant blends were compacted into cylindrical preforms and extruded through a die having a circular orifice and a reduction ratio of 900:1. The resultant bead extrudates required the extrusion pressures shown in Table 1. It can be seen from Table 1 that extrusion pressure is substantially decreased by the addition of a small amount of the curable silicone polymer, yet all of the extrudate samples appeared to be the same to the eye and had the normal feel of PTFE dispersion grade resin extrusions. Samples 5 and 6 show an increase in extrusion pressure when compared to Samples 2 and 3, respectively, due to a reduction in organic lubricant content.

              TABLE 1______________________________________Sample PTFE    Silicone VM & P naptha                            Extrusion PressureNo.   (g.)    (g.)     (g.)      (psi)______________________________________1-1   3178     0       699.2     8,7501-2   3114.4   63.6    699.2     7,1101-3   3019.1  158.9    699.2     5,7701-4   2955.5  222.5    699.2     3,8001-5   3114.4   63.6    607.0     11,7001-6   3019.1  158.9    562.5     7.520______________________________________
EXAMPLE 2

Three kerosene/PTFE dispersion grade resin blends and four silicone/kerosene/PTFE dispersion grade resin blends were prepared using a liquid-solids blender and the silicone composition and PTFE resin of Example 1. The resultant blends were compacted into cylindrical preforms and extruded through a die constructed to achieve biaxial fibrillation as described in U.S. Pat. No. 3,315,020. The extrudates of Samples 2-1, 2-2, 2-3 and 2-4 were calendered to 5 mil thicknesses and samples 2-5, 2-6 and 2-7 were calendered to 4 mil thicknesses. Each extrudate was heated at between 310° F. and 320° F. to evaporate the kerosene and to cure the silicone elastomer. The extrusion conditions and physical properties of the extrudates are shown in Table 2. By comparing Sample Nos. 2-1, 2-2 and 2-5 with Sample Nos. 2-3, 2-4 and 2-7, it can be seen that the density of the extrudates incorporating silicone elastomer was increased by as much as 28% over that of the comparable PTFE extrudate. It can also be seen that incorporation of silicone elastomer in the biaxially fibrillated extrudates improved the transverse elongation before break property as much as 37.5% of the value without silicone elastomer incorporation.

EXAMPLE 3

The extrudates obtained according to Example 2 were transversely stretched using a tenter frame. The samples incorporating silicone elastomer were heated at about 120° C. during stretching while the PTFE extrudates were heated at 175° C. during stretching. Physical properties of the resultant microporous films obtained are shown in Table 3. It can be seen in each case that the incorporation of silicone elastomer increased tensile strengths of the stretched products in both machine direction and transverse direction. A scanning electron micro-photograph of stretched Sample 2-3 was taken at 5,000X magnification and is shown in the drawing. The random fibrillations shown have thicknesses as large as 1.0 micron.

                                  TABLE 2__________________________________________________________________________                           transverse                           direction              extrusion                   linear  tensile                                 T.D.ExtrusionPTFE    Silicone         Kerosene              pressure                   stretch                       density                           strength                                 elongationNo.  (g.)    (g.) (g.) (psi)                   ratio                       (g/cc)                           (psi) (%)__________________________________________________________________________Reduction ratio = 12.3:1Extrusion width = 8 inches2-1  3178     0   619.2              4000 1:1 1.57                           367   10002-2  3178     0   619.2              4000 1.84:1                       1.03                           233   14002-3  2955.5    222.5         590.3              4600 1.1 1.69                           440   11502-4  2955.5    222.5         540.3              4600 1.84:1                       1.32                           293   1350Reduction ratio = 8.18:1Extrusion width = 12 inches2-5  3178     0   826.3              2600 1.84:1                       1.05                           192    8002-6  2955.5    222.5         730.9              2600 1:1 1.74                           390    9002-7  2955.5    222.5         730.9              2600 1.84:1                       1.31                           259   1100__________________________________________________________________________

              TABLE 3______________________________________                Tensile Strength                (psi)                              Trans- Extru-  %      Linear                      Transverse                              verseSample sion    Sili-  Stretch                      Stretch Direc- MachineNo.   No.     cone   Ratio (%)     tion   Direction______________________________________3-1   2-1     0      1.1   1278    1260    6853-2   2-2     0      1.84:1                      1278    1830   14803-3   2-2     0      1.84:1                      1544    1300    8893-4   2-3     7      1.1   1278    1890    9863-5   2-3     7      1.1   1767    1550    9143-6   2-4     7      1.84:1                      1278    2180   21103-7   2-4     7      1.84:1                      1544    1980   17103-8   2-5     0      1.84:1                       825     919   11003-9   2-6     7      1.84:1                       825    1940    720 3-10 2-7     7      1.1    675    1740   2850 3-11 2-7     7      1.84:1                       825    1590   1700______________________________________
EXAMPLE 4

Five portions of the microporous film Sample No. 3-6, produced in accordance with Example 3, were sprayed continuously for 15 seconds with a low-odor kerosene solution of the curable silicone composition set forth in Example 1 at increasing silicone concentrations (2.5%, 5.0%, 10.0%, 15.0%, 20.0%). After spraying and evaporation of the solvent, the samples were cured at 150° C. for 15 minutes. Table 4 shows the surprising effect of this cured silicone elastomer impregnation of microporous film products formed from the polymer network compositions of this invention on the opacity of the film as compared to the untreated film. Other physical characteristics of these products are likewise shown in Table 4.

                                  TABLE 4__________________________________________________________________________                  hydro-                  static                      vapor  moisture    %    amount        resist-                      trans- Tappi                                  GurleySample    solution    deposited         thickness              density                  ance                      mission                             opacity                                  numberNo. sprayed    (mg/cm.sup.2)         (mil)              (g/cc)                  (psi)                      (g/m.sup.2 /24 hrs)                             (%)  (seconds)__________________________________________________________________________3-6 --   --   1.3  0.33                  77  701    73.8  64-1 2.5  0.11 0.5  0.95                  82  736    49.0 444-2 5    0.26 0.5  1.07                  82  755    50.1 644-3 10   0.33 0.4  1.13                  84  764    36.7 904-4 15   0.38 0.5  1.17                  91  720    35.3 1164-5 20   0.70 0.6  1.18                  125 638    16.8 1128__________________________________________________________________________

______________________________________Example 5The following ingredients were blended together using aliquid-solids blender:238.4 g      Silicone composition of Example 1238.4 g      Calcium carbonate2701.3 g     PTFE dispersion grade resin730.9 g      Kerosene______________________________________

The resultant blend was then compacted into cylindrical preforms and extruded through the die utilized in the extrusion of Samples 2-1 through 2-4. An extrusion pressure of 3,000 psi was observed. The extrudate was calendered to a 5 mil thickness and then heated at between 310° F. and 320° F. to evaporate the kerosene and to cure the silicone elastomer. It is apparent from this example that the process of this invention can be utilized to produce filled semi-interpenetrating polymer networks of PTFE and silicone elastomers.

Claims (5)

Having thus described our invention, we claim:
1. A process for producing a semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomers which comprises the steps of (1) intimately blending a mixture of a major amount of unsintered and unfibrillated particulate polytetrafluoroethylene dispersion resin and minor amounts of (A) a hydrocarbon liquid and (B) an addition curable silicone composition consisting essentially of a polydiorganosiloxane having alkenyl unsaturation, an organohydrogenpolysiloxane crosslinking agent, a catalyst for promoting crosslinking of said polysiloxane, and an inhibitor for the catalytic reaction; (2) forming said blend into an extrudable shape; (3) biaxially extruding said blend through a die into a shaped extrudate product having a randomly fibrillated structure; (4) evaporating said hydrocarbon liquid, and activating said catalyst so as to generate a cured silicone elastomer and polytetrafluoroethylene semi-interpenetrating polymer network comprising said fibrillated extrudate structure.
2. The process of claim 1 further characterized by calendering the shaped extrudate product to a uniform thickness.
3. The process of claim 1 wherein the amount of addition curable silicone composition constitutes at least two percent by weight of the mixture of polytetrafluoroethylene, hydrocarbon liquid and addition curable silicone composition.
4. The process of claim 1, wherein the mixture of step (1) includes additionally a minor amount of calcium carbonate.
5. The product of the process of claim 1.
US07000389 1987-01-05 1987-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof Expired - Lifetime US4945125A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US07000389 US4945125A (en) 1987-01-05 1987-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
US07000389 US4945125A (en) 1987-01-05 1987-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof
CA 555735 CA1326099C (en) 1987-01-05 1988-01-04 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof
EP19880901354 EP0296240B1 (en) 1987-01-05 1988-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof
PCT/US1988/000062 WO1988004982A1 (en) 1987-01-05 1988-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof
DE19883870048 DE3870048D1 (en) 1987-01-05 1988-01-05 A process for the manufacture of shaped fibrillated halbinterpenetrierendem polymer network of polytetrafluoroethylene and silicone elastomer and from these materials products.
KR880070959A KR960006795B1 (en) 1987-01-05 1988-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer
CN 88100643 CN1014795B (en) 1987-01-05 1988-01-05 Process for producing fibrillated semi-inter-penetrating polymer network of ptfe and silicone elastomer and shaped products thereof
JP50633987A JPH0726311B2 (en) 1987-01-05 1988-01-05 Manufacturing method and molded product of the fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer
FI883962A FI91644C (en) 1987-01-05 1988-08-26 Process for the preparation of fibrillated formed, semi-interpenetrating polymer network of polytetrafluoroethylene and silicone, and molded products prepared from
DK492988A DK174355B1 (en) 1987-01-05 1988-09-05 Fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and siliconeelatomer as well as method for preparation thereof
US07518435 US5066683A (en) 1987-01-05 1990-05-01 Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US07713029 US5157058A (en) 1987-01-05 1991-06-07 Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US08113732 US5362553A (en) 1987-01-05 1993-08-27 Microporous waterproof and moisture vapor permeable fabric

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US07518435 Continuation-In-Part US5066683A (en) 1987-01-05 1990-05-01 Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof

Publications (1)

Publication Number Publication Date
US4945125A true US4945125A (en) 1990-07-31

Family

ID=21691323

Family Applications (1)

Application Number Title Priority Date Filing Date
US07000389 Expired - Lifetime US4945125A (en) 1987-01-05 1987-01-05 Process of producing a fibrillated semi-interpenetrating polymer network of polytetrafluoroethylene and silicone elastomer and shaped products thereof

Country Status (10)

Country Link
US (1) US4945125A (en)
JP (1) JPH0726311B2 (en)
KR (1) KR960006795B1 (en)
CN (1) CN1014795B (en)
CA (1) CA1326099C (en)
DE (1) DE3870048D1 (en)
DK (1) DK174355B1 (en)
EP (1) EP0296240B1 (en)
FI (1) FI91644C (en)
WO (1) WO1988004982A1 (en)

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991017205A1 (en) * 1990-05-01 1991-11-14 Tetratec Corporation Improved microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5157058A (en) * 1987-01-05 1992-10-20 Tetratec Corporation Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5209967A (en) * 1992-01-31 1993-05-11 Minnesota Mining And Manufacturing Company Pressure sensitive membrane and method therefor
US5238621A (en) * 1991-06-28 1993-08-24 Minnesota Mining And Manufacturing Company Method of controlling porosity in a composite article
US5248428A (en) * 1991-06-28 1993-09-28 Minnesota Mining And Manufacturing Company Article for separations and purifications and method of controlling porosity therein
US5328756A (en) * 1992-01-31 1994-07-12 Minnesota Mining And Manufacturing Company Temperature sensitive circuit breaking element
US5362553A (en) * 1987-01-05 1994-11-08 Tetratec Corporation Microporous waterproof and moisture vapor permeable fabric
US5411351A (en) * 1989-08-28 1995-05-02 Minnesota Mining And Manufacturing Company Conforming a microporous sheet to a solid surface
US5411576A (en) * 1993-03-26 1995-05-02 Minnesota Mining And Manufacturing Company Oily mist resistant electret filter media and method for filtering
US5428097A (en) * 1993-03-31 1995-06-27 Dow Corning Toray Silicon Co., Ltd. Silicone rubber composition
US5529820A (en) * 1993-03-17 1996-06-25 Japan Gore-Tex, Inc. Flexible, non-porous tube and a method of making
WO1996022621A1 (en) * 1995-01-19 1996-07-25 W. L. Gore & Associates, Inc. Electrical interconnect assemblies
WO1997009167A1 (en) * 1995-09-05 1997-03-13 Bio Med Sciences, Inc. Microporous membrane with a stratified pore structure created in situ and process
EP0779629A2 (en) * 1995-12-15 1997-06-18 W.L. GORE & ASSOCIATES, INC. Electrically conductive polytetrafluoroethylene article
US5656279A (en) * 1994-02-23 1997-08-12 Bio Med Sciences, Inc. Semi-interpenetrating polymer network scar treatment sheeting, process of manufacture and useful articles thereof
WO1998027419A1 (en) 1996-12-19 1998-06-25 Implanted Biosystems, Inc. Glucose sensor
WO1998030891A1 (en) 1997-01-06 1998-07-16 Implanted Biosystems, Inc. Implantable sensor employing an auxiliary electrode
US5789047A (en) * 1993-12-21 1998-08-04 Japan Gore-Tex, Inc Flexible, multilayered tube
US5846355A (en) * 1994-09-13 1998-12-08 W. L. Gore & Associates, Inc. Jacket material for protection of electrical conductors
US5869156A (en) * 1991-06-04 1999-02-09 Donaldson Company, Inc. Porous products manufactured from polytetrafluoroethylene treated with a perfluoroether fluid and method of manufacturing such products
US5886101A (en) * 1988-03-02 1999-03-23 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
US5945217A (en) * 1997-10-14 1999-08-31 Gore Enterprise Holdings, Inc. Thermally conductive polytrafluoroethylene article
US6123751A (en) * 1998-06-09 2000-09-26 Donaldson Company, Inc. Filter construction resistant to the passage of water soluble materials; and method
US6127474A (en) * 1997-08-27 2000-10-03 Andelman; Marc D. Strengthened conductive polymer stabilized electrode composition and method of preparing
WO2001019914A1 (en) * 1998-09-08 2001-03-22 Dow Corning Corporation Thermoplastic silicone elastomers based on fluorocarbon resin
US6284192B1 (en) * 1998-11-02 2001-09-04 Corning Incorporated Extruding electrode material
EP1227373A1 (en) * 2001-01-30 2002-07-31 Xerox Corporation An interpenetrating polymer network of polytetra fluoroethylene and silicone elastomer for use in electrophotographic fusing applications
US6451396B1 (en) * 1998-02-13 2002-09-17 Gore Enterprise Holdings, Inc. Flexure endurant composite elastomer compositions
US6517919B1 (en) 1998-07-10 2003-02-11 Donaldson Company, Inc. Laminate and pulse jet filter bag
US20040063803A1 (en) * 2002-09-27 2004-04-01 Kim Hyum Jin Polymer networks comprising silicone and methods for making them
US6770086B1 (en) 2000-11-02 2004-08-03 Scimed Life Systems, Inc. Stent covering formed of porous polytetraflouroethylene
US20050025985A1 (en) * 2003-07-29 2005-02-03 Parker Richard Henry Polymer coating blends
US20050124256A1 (en) * 2003-12-09 2005-06-09 Vanessa Mason Synthetic insulation with microporous membrane
US20050167875A1 (en) * 2002-05-02 2005-08-04 Fumihiro Hayashi Stretched polytetrafluoroethylene moldings and process for production thereof
US20050191169A1 (en) * 2004-03-01 2005-09-01 Cuvelier Leon R. Silencer for ventilation system and methods
US20060041091A1 (en) * 1999-01-19 2006-02-23 Chang James W Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US20060112825A1 (en) * 2004-11-30 2006-06-01 Dominique Renwart Gas turbine air intake system with bypass arrangement and methods
US20060118236A1 (en) * 2004-11-29 2006-06-08 House Wayne D Implantable devices with reduced needle puncture site leakage
US20060157893A1 (en) * 2004-11-24 2006-07-20 Kirit Patel PTFE membrane
US20080036183A1 (en) * 2006-08-10 2008-02-14 Ramesh Keshavaraj Airbag coatings made with hybrid resin compositions
US20080105629A1 (en) * 2006-11-08 2008-05-08 Donaldson Company, Inc. Systems, articles, and methods for removing water from hydrocarbon fluids
US20080173179A1 (en) * 2007-01-18 2008-07-24 Kunj Tandon Composite membrane for separation of carbon dioxide
US20080257153A1 (en) * 2007-04-23 2008-10-23 Harp Gary P Patterned Porous Venting Materials
US20080257155A1 (en) * 2007-04-23 2008-10-23 Bacino John E Porous Composite Article
US20090014338A1 (en) * 2005-06-07 2009-01-15 Canon Kabushiki Kaisha Structure, porous body, sensor, process of structure and detecting mehod for specimen
US20090061205A1 (en) * 2007-09-04 2009-03-05 Fujifilm Corporation Crystalline polymer microporous film, manufacturing method of the same, and filtration filter
US20090159526A1 (en) * 2006-05-19 2009-06-25 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing same, and filter for filtration
DE102009003407A1 (en) 2008-01-29 2009-07-30 General Electric Co. A method for increasing the oleophobicity by PTEE and resultant oleophobic articles
US20100051535A1 (en) * 2008-09-02 2010-03-04 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing the same, and filter for filtration
US20100062043A1 (en) * 2008-07-15 2010-03-11 Basf Catalysts Llc Methods, Systems and Devices for Administration of Chlorine Dioxide
US20100198136A1 (en) * 2009-02-04 2010-08-05 Basf Catalysts Llc Chlorine Dioxide Treatment for Biological Tissue
US8048440B2 (en) 2002-08-05 2011-11-01 Gore Enterprise Holdings, Inc. Thermoplastic fluoropolymer-coated medical devices
US8075669B2 (en) 2007-04-23 2011-12-13 Gore Enterprise Holdings, Inc. Composite material
US8721756B2 (en) 2008-06-13 2014-05-13 Donaldson Company, Inc. Filter construction for use with air in-take for gas turbine and methods
US8808848B2 (en) 2010-09-10 2014-08-19 W. L. Gore & Associates, Inc. Porous article
US9101562B2 (en) 2010-01-31 2015-08-11 Basf Corporation Additives for chlorine dioxide-containing compositions
US9427710B2 (en) 2013-03-15 2016-08-30 Bemis Company, Inc. Radial filtration vent and medical device packaging
US9570773B2 (en) 2010-10-07 2017-02-14 Asahi Kasei E-Materials Corporation Fluorine-based polymer electrolyte membrane
US9814560B2 (en) 2013-12-05 2017-11-14 W. L. Gore & Associates, Inc. Tapered implantable device and methods for making such devices

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831071A (en) * 1987-09-21 1989-05-16 Ici Americas Inc. Enhanced melt extrusion of thermoplastics containing silicone interpenetrating polymer networks
US6004679A (en) * 1991-03-14 1999-12-21 General Electric Company Laminates containing addition-curable silicone adhesive compositions
US5164461A (en) * 1991-03-14 1992-11-17 General Electric Company Addition-curable silicone adhesive compositions
US5643516A (en) * 1993-08-12 1997-07-01 U.S. Farathane Corporation Process for manufacturing polyurethane products
US5552100A (en) * 1995-05-02 1996-09-03 Baxter International Inc. Method for manufacturing porous fluoropolymer films
WO1997022661A1 (en) * 1995-12-15 1997-06-26 W.L. Gore & Associates, Inc. Improved polytetrafluoroethylene article
US6099791A (en) * 1996-03-08 2000-08-08 Baxter International Inc. Methods of manufacture of multiaxially oriented fluoropolymer films
DE102008040133A1 (en) 2008-07-03 2010-01-07 Leibniz-Institut Für Polymerforschung Dresden E.V. Polychloroprene-perfluoropolymer-material, useful e.g. as compact substances, comprises melt produced by reacting polychloroprene matrix with modified perfluoropolymer particles, that are chemically linked via covalent bond with the matrix

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2710290A (en) * 1953-04-03 1955-06-07 Gen Electric Organopolysiloxane-polytetrafluoroethylene mixtures
US2927908A (en) * 1960-03-08 Fluorinated organopolysiloxane rub-
US3278673A (en) * 1963-09-06 1966-10-11 Gore & Ass Conductor insulated with polytetra-fluoroethylene containing a dielectric-dispersionand method of making same
US3293203A (en) * 1962-03-26 1966-12-20 Acheson Ind Inc Thermosettable resin compositions and method for forming low friction surface coatings
US3315020A (en) * 1962-03-21 1967-04-18 Gore & Ass Process for preparing biaxially fibrillated sheets
US3325434A (en) * 1961-07-20 1967-06-13 Gen Electric Polytetrafluoroethylene-silicone rubber extrusion composition
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3528879A (en) * 1963-10-14 1970-09-15 Daikin Ind Ltd Process for making paper and air-pervious cardboard or boardlike structures predominantly of polytetrafluoroethylene
US4042747A (en) * 1975-03-14 1977-08-16 Joseph A. Teti, Jr. Gasket and sealing structures of filled polytetrafluoroethylene resins
US4153661A (en) * 1977-08-25 1979-05-08 Minnesota Mining And Manufacturing Company Method of making polytetrafluoroethylene composite sheet
US4183887A (en) * 1977-04-28 1980-01-15 Copolymer Rubber & Chemical Corporation Method for producing free flowing particles of elastomeric material
US4194040A (en) * 1969-04-23 1980-03-18 Joseph A. Teti, Jr. Article of fibrillated polytetrafluoroethylene containing high volumes of particulate material and methods of making and using same
US4482516A (en) * 1982-09-10 1984-11-13 W. L. Gore & Associates, Inc. Process for producing a high strength porous polytetrafluoroethylene product having a coarse microstructure
US4500688A (en) * 1982-04-20 1985-02-19 Petrarch Systems Inc. Curable silicone containing compositions and methods of making same
US4596839A (en) * 1981-09-16 1986-06-24 Peters William E Elastomer PTFE composition
US4764560A (en) * 1985-11-13 1988-08-16 General Electric Company Interpenetrating polymeric network comprising polytetrafluoroethylene and polysiloxane

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1283492C (en) * 1985-11-13 1991-04-23 Tyrone D. Mitchell Interpenetrating polymeric networks comprising polytetrafluoroethylene and polysiloxane

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2927908A (en) * 1960-03-08 Fluorinated organopolysiloxane rub-
US2710290A (en) * 1953-04-03 1955-06-07 Gen Electric Organopolysiloxane-polytetrafluoroethylene mixtures
US3382305A (en) * 1954-10-29 1968-05-07 Du Pont Process for preparing oriented microfibers
US3325434A (en) * 1961-07-20 1967-06-13 Gen Electric Polytetrafluoroethylene-silicone rubber extrusion composition
US3315020A (en) * 1962-03-21 1967-04-18 Gore & Ass Process for preparing biaxially fibrillated sheets
US3293203A (en) * 1962-03-26 1966-12-20 Acheson Ind Inc Thermosettable resin compositions and method for forming low friction surface coatings
US3278673A (en) * 1963-09-06 1966-10-11 Gore & Ass Conductor insulated with polytetra-fluoroethylene containing a dielectric-dispersionand method of making same
US3528879A (en) * 1963-10-14 1970-09-15 Daikin Ind Ltd Process for making paper and air-pervious cardboard or boardlike structures predominantly of polytetrafluoroethylene
US4194040A (en) * 1969-04-23 1980-03-18 Joseph A. Teti, Jr. Article of fibrillated polytetrafluoroethylene containing high volumes of particulate material and methods of making and using same
US4042747A (en) * 1975-03-14 1977-08-16 Joseph A. Teti, Jr. Gasket and sealing structures of filled polytetrafluoroethylene resins
US4183887A (en) * 1977-04-28 1980-01-15 Copolymer Rubber & Chemical Corporation Method for producing free flowing particles of elastomeric material
US4153661A (en) * 1977-08-25 1979-05-08 Minnesota Mining And Manufacturing Company Method of making polytetrafluoroethylene composite sheet
US4596839A (en) * 1981-09-16 1986-06-24 Peters William E Elastomer PTFE composition
US4500688A (en) * 1982-04-20 1985-02-19 Petrarch Systems Inc. Curable silicone containing compositions and methods of making same
US4482516A (en) * 1982-09-10 1984-11-13 W. L. Gore & Associates, Inc. Process for producing a high strength porous polytetrafluoroethylene product having a coarse microstructure
US4764560A (en) * 1985-11-13 1988-08-16 General Electric Company Interpenetrating polymeric network comprising polytetrafluoroethylene and polysiloxane

Cited By (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5362553A (en) * 1987-01-05 1994-11-08 Tetratec Corporation Microporous waterproof and moisture vapor permeable fabric
US5066683A (en) * 1987-01-05 1991-11-19 Tetratec Corporation Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5157058A (en) * 1987-01-05 1992-10-20 Tetratec Corporation Microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5886101A (en) * 1988-03-02 1999-03-23 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
US5985998A (en) * 1988-03-02 1999-11-16 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
US6228919B1 (en) 1988-03-02 2001-05-08 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
US5411351A (en) * 1989-08-28 1995-05-02 Minnesota Mining And Manufacturing Company Conforming a microporous sheet to a solid surface
WO1991017205A1 (en) * 1990-05-01 1991-11-14 Tetratec Corporation Improved microporous waterproof and moisture vapor permeable structures, processes of manufacture and useful articles thereof
US5972449A (en) * 1991-06-04 1999-10-26 Donaldson Company, Inc. Porous products manufactured from polytetrafluoroethylene treated with a perfluoroether fluid and methods of manufacturing such products
US5869156A (en) * 1991-06-04 1999-02-09 Donaldson Company, Inc. Porous products manufactured from polytetrafluoroethylene treated with a perfluoroether fluid and method of manufacturing such products
US5248428A (en) * 1991-06-28 1993-09-28 Minnesota Mining And Manufacturing Company Article for separations and purifications and method of controlling porosity therein
US5238621A (en) * 1991-06-28 1993-08-24 Minnesota Mining And Manufacturing Company Method of controlling porosity in a composite article
US5209967A (en) * 1992-01-31 1993-05-11 Minnesota Mining And Manufacturing Company Pressure sensitive membrane and method therefor
US5328756A (en) * 1992-01-31 1994-07-12 Minnesota Mining And Manufacturing Company Temperature sensitive circuit breaking element
US5529820A (en) * 1993-03-17 1996-06-25 Japan Gore-Tex, Inc. Flexible, non-porous tube and a method of making
US5472481A (en) * 1993-03-26 1995-12-05 Minnesota Mining And Manufacturing Company Oily mist resistant electret filter media
US5411576A (en) * 1993-03-26 1995-05-02 Minnesota Mining And Manufacturing Company Oily mist resistant electret filter media and method for filtering
US5428097A (en) * 1993-03-31 1995-06-27 Dow Corning Toray Silicon Co., Ltd. Silicone rubber composition
US5789047A (en) * 1993-12-21 1998-08-04 Japan Gore-Tex, Inc Flexible, multilayered tube
US5656279A (en) * 1994-02-23 1997-08-12 Bio Med Sciences, Inc. Semi-interpenetrating polymer network scar treatment sheeting, process of manufacture and useful articles thereof
US5980923A (en) * 1994-02-23 1999-11-09 Bio Med Sciences, Inc. Semi-interpenetrating polymer network scar treatment sheeting, process of manufacture and useful articles thereof
US5846355A (en) * 1994-09-13 1998-12-08 W. L. Gore & Associates, Inc. Jacket material for protection of electrical conductors
WO1996022621A1 (en) * 1995-01-19 1996-07-25 W. L. Gore & Associates, Inc. Electrical interconnect assemblies
WO1997009167A1 (en) * 1995-09-05 1997-03-13 Bio Med Sciences, Inc. Microporous membrane with a stratified pore structure created in situ and process
US6235377B1 (en) 1995-09-05 2001-05-22 Bio Med Sciences, Inc. Microporous membrane with a stratified pore structure created in situ and process
EP0779629A2 (en) * 1995-12-15 1997-06-18 W.L. GORE & ASSOCIATES, INC. Electrically conductive polytetrafluoroethylene article
EP0779629A3 (en) * 1995-12-15 1997-08-06 W.L. GORE & ASSOCIATES, INC. Electrically conductive polytetrafluoroethylene article
US5964993A (en) * 1996-12-19 1999-10-12 Implanted Biosystems Inc. Glucose sensor
WO1998027419A1 (en) 1996-12-19 1998-06-25 Implanted Biosystems, Inc. Glucose sensor
EP1021706A1 (en) * 1997-01-06 2000-07-26 Implanted Biosystems, Inc. Implantable sensor employing an auxiliary electrode
WO1998030891A1 (en) 1997-01-06 1998-07-16 Implanted Biosystems, Inc. Implantable sensor employing an auxiliary electrode
US5914026A (en) * 1997-01-06 1999-06-22 Implanted Biosystems Inc. Implantable sensor employing an auxiliary electrode
US6127474A (en) * 1997-08-27 2000-10-03 Andelman; Marc D. Strengthened conductive polymer stabilized electrode composition and method of preparing
US5945217A (en) * 1997-10-14 1999-08-31 Gore Enterprise Holdings, Inc. Thermally conductive polytrafluoroethylene article
US6673455B2 (en) * 1998-02-13 2004-01-06 Gore Enterprise Holdings Inc. Flexure endurant composite elastomer compositions
US6451396B1 (en) * 1998-02-13 2002-09-17 Gore Enterprise Holdings, Inc. Flexure endurant composite elastomer compositions
US6123751A (en) * 1998-06-09 2000-09-26 Donaldson Company, Inc. Filter construction resistant to the passage of water soluble materials; and method
US6368386B1 (en) * 1998-06-09 2002-04-09 Donaldson Company, Inc. Filter construction resistant to the passage of water soluble materials; and method
US6517919B1 (en) 1998-07-10 2003-02-11 Donaldson Company, Inc. Laminate and pulse jet filter bag
WO2001019914A1 (en) * 1998-09-08 2001-03-22 Dow Corning Corporation Thermoplastic silicone elastomers based on fluorocarbon resin
US6284192B1 (en) * 1998-11-02 2001-09-04 Corning Incorporated Extruding electrode material
US20060041091A1 (en) * 1999-01-19 2006-02-23 Chang James W Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US7462675B2 (en) 1999-01-19 2008-12-09 Gore Enterprise Holdings, Inc. Thermoplastic copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether and medical devices employing the copolymer
US6770086B1 (en) 2000-11-02 2004-08-03 Scimed Life Systems, Inc. Stent covering formed of porous polytetraflouroethylene
US20040220659A1 (en) * 2000-11-02 2004-11-04 Scimed Life Systems, Inc. Stent covering formed of porous polytetraflouroethylene
EP1227373A1 (en) * 2001-01-30 2002-07-31 Xerox Corporation An interpenetrating polymer network of polytetra fluoroethylene and silicone elastomer for use in electrophotographic fusing applications
US6447918B1 (en) 2001-01-30 2002-09-10 Xerox Corporation Interpenetrating polymer network of polytetra fluoroethylene and silicone elastomer for use in electrophotographic fusing applications
US20050167875A1 (en) * 2002-05-02 2005-08-04 Fumihiro Hayashi Stretched polytetrafluoroethylene moldings and process for production thereof
US7691299B2 (en) * 2002-05-02 2010-04-06 Sumitomo Electric Industries, Ltd. Process for production of expanded polytetrafluoroetylene products
US8609125B2 (en) 2002-08-05 2013-12-17 W. L. Gore & Associates, Inc. Thermoplastic fluoropolymer-coated medical devices
US8048440B2 (en) 2002-08-05 2011-11-01 Gore Enterprise Holdings, Inc. Thermoplastic fluoropolymer-coated medical devices
US20040063803A1 (en) * 2002-09-27 2004-04-01 Kim Hyum Jin Polymer networks comprising silicone and methods for making them
US7026399B2 (en) 2002-09-27 2006-04-11 Taylor Made Golf Company, Inc. Golf ball incorporating a polymer network comprising silicone
US7132170B2 (en) * 2003-07-29 2006-11-07 Milliken & Company Polymer coating blends
US20050025985A1 (en) * 2003-07-29 2005-02-03 Parker Richard Henry Polymer coating blends
US20050124256A1 (en) * 2003-12-09 2005-06-09 Vanessa Mason Synthetic insulation with microporous membrane
US9185941B2 (en) 2003-12-09 2015-11-17 Primaloft, Inc. Synthetic insulation with microporous membrane
US20050191169A1 (en) * 2004-03-01 2005-09-01 Cuvelier Leon R. Silencer for ventilation system and methods
US7048500B2 (en) 2004-03-01 2006-05-23 Donaldson Company, Inc. Silencer for ventilation system and methods
US9409132B2 (en) 2004-11-24 2016-08-09 Donaldson Company, Inc. PTFE membrane
US20060157893A1 (en) * 2004-11-24 2006-07-20 Kirit Patel PTFE membrane
US7922946B2 (en) 2004-11-24 2011-04-12 Donaldson Company, Inc. PTFE membrane
US20060118236A1 (en) * 2004-11-29 2006-06-08 House Wayne D Implantable devices with reduced needle puncture site leakage
US8906087B2 (en) 2004-11-29 2014-12-09 W. L. Gore & Associates, Inc. Method of making implantable devices with reduced needle puncture site leakage
US8029563B2 (en) 2004-11-29 2011-10-04 Gore Enterprise Holdings, Inc. Implantable devices with reduced needle puncture site leakage
US20060112825A1 (en) * 2004-11-30 2006-06-01 Dominique Renwart Gas turbine air intake system with bypass arrangement and methods
US7297173B2 (en) 2004-11-30 2007-11-20 Donaldson Company, Inc. Gas turbine air intake system with bypass arrangement and methods
US7914663B2 (en) * 2005-06-07 2011-03-29 Canon Kabushiki Kaisha Structure, porous body, sensor, process of structure and detecting method for specimen
US20090014338A1 (en) * 2005-06-07 2009-01-15 Canon Kabushiki Kaisha Structure, porous body, sensor, process of structure and detecting mehod for specimen
US20090159526A1 (en) * 2006-05-19 2009-06-25 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing same, and filter for filtration
US8153041B2 (en) 2006-05-19 2012-04-10 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing same, and filter for filtration
US20110049044A1 (en) * 2006-05-19 2011-03-03 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing the same, an dfilter for filtration
US7543843B2 (en) 2006-08-10 2009-06-09 Milliken & Company Airbag coatings made with hybrid resin compositions
US20080036183A1 (en) * 2006-08-10 2008-02-14 Ramesh Keshavaraj Airbag coatings made with hybrid resin compositions
US9795897B2 (en) 2006-11-08 2017-10-24 Donaldson Company, Inc. Systems, articles, and methods for removing water from hydrocarbon fluids
US20080105629A1 (en) * 2006-11-08 2008-05-08 Donaldson Company, Inc. Systems, articles, and methods for removing water from hydrocarbon fluids
US7811359B2 (en) * 2007-01-18 2010-10-12 General Electric Company Composite membrane for separation of carbon dioxide
US20080173179A1 (en) * 2007-01-18 2008-07-24 Kunj Tandon Composite membrane for separation of carbon dioxide
US8075669B2 (en) 2007-04-23 2011-12-13 Gore Enterprise Holdings, Inc. Composite material
US7927405B2 (en) 2007-04-23 2011-04-19 Gore Enterprise Holdings, Inc Porous composite article
US20080257153A1 (en) * 2007-04-23 2008-10-23 Harp Gary P Patterned Porous Venting Materials
US20080257155A1 (en) * 2007-04-23 2008-10-23 Bacino John E Porous Composite Article
US8858681B2 (en) 2007-04-23 2014-10-14 W. L. Gore & Associates, Inc. Patterned porous venting materials
US8011518B2 (en) * 2007-09-04 2011-09-06 Fujifilm Corporation Crystalline polymer microporous film, manufacturing method of the same, and filtration filter
US20090061205A1 (en) * 2007-09-04 2009-03-05 Fujifilm Corporation Crystalline polymer microporous film, manufacturing method of the same, and filtration filter
US20090191397A1 (en) * 2008-01-29 2009-07-30 General Electric Company Process to increase the oleophobicity of ptfe, and resulting oleophobic articles
US8088445B2 (en) 2008-01-29 2012-01-03 General Electric Company Process to increase the oleophobicity of PTFE, and resulting oleophobic articles
DE102009003407A1 (en) 2008-01-29 2009-07-30 General Electric Co. A method for increasing the oleophobicity by PTEE and resultant oleophobic articles
US8721756B2 (en) 2008-06-13 2014-05-13 Donaldson Company, Inc. Filter construction for use with air in-take for gas turbine and methods
US20100112059A1 (en) * 2008-07-15 2010-05-06 Basf Catalysts Llc Methods, Systems and Devices for Administration of Chlorine Dioxide
US20100062043A1 (en) * 2008-07-15 2010-03-11 Basf Catalysts Llc Methods, Systems and Devices for Administration of Chlorine Dioxide
US20100051535A1 (en) * 2008-09-02 2010-03-04 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing the same, and filter for filtration
US8151998B2 (en) * 2008-09-02 2012-04-10 Fujifilm Corporation Crystalline polymer microporous membrane, method for producing the same, and filter for filtration
US20100196512A1 (en) * 2009-02-04 2010-08-05 Basf Catalyst Llc Treatment of Non-Oral Biological Tissue with Chlorine Dioxide
US8703106B2 (en) 2009-02-04 2014-04-22 Basf Corporation Chlorine dioxide treatment for biological tissue
US20100198136A1 (en) * 2009-02-04 2010-08-05 Basf Catalysts Llc Chlorine Dioxide Treatment for Biological Tissue
US8311625B2 (en) 2009-02-04 2012-11-13 Basf Corporation Chlorine dioxide treatment for biological tissue
US9101562B2 (en) 2010-01-31 2015-08-11 Basf Corporation Additives for chlorine dioxide-containing compositions
US8808848B2 (en) 2010-09-10 2014-08-19 W. L. Gore & Associates, Inc. Porous article
US9570773B2 (en) 2010-10-07 2017-02-14 Asahi Kasei E-Materials Corporation Fluorine-based polymer electrolyte membrane
US9427710B2 (en) 2013-03-15 2016-08-30 Bemis Company, Inc. Radial filtration vent and medical device packaging
US9814560B2 (en) 2013-12-05 2017-11-14 W. L. Gore & Associates, Inc. Tapered implantable device and methods for making such devices

Also Published As

Publication number Publication date Type
JPH0726311B2 (en) 1995-03-22 grant
FI91644C (en) 1994-07-25 grant
DK492988A (en) 1988-09-05 application
DE3870048D1 (en) 1992-05-21 grant
JPH01501876A (en) 1989-06-29 application
FI883962D0 (en) grant
FI91644B (en) 1994-04-15 application
EP0296240A1 (en) 1988-12-28 application
KR960006795B1 (en) 1996-05-23 grant
CA1326099C (en) 1994-01-11 grant
CN88100643A (en) 1988-11-02 application
FI883962A0 (en) 1988-08-26 application
DK174355B1 (en) 2002-12-30 grant
CN1014795B (en) 1991-11-20 application
EP0296240A4 (en) 1989-04-27 application
FI883962A (en) 1988-08-26 application
EP0296240B1 (en) 1992-04-15 grant
DK492988D0 (en) 1988-09-05 grant
WO1988004982A1 (en) 1988-07-14 application

Similar Documents

Publication Publication Date Title
US3372049A (en) Polyolefin film composition, film, and pressure-sensitive adhesive sheet material
US4545950A (en) Process for producing stretched articles of ultrahigh-molecular-weight polyethylene
US4791144A (en) Microporous film and process for production thereof
US4902456A (en) Fluorocarbon membranes and process for making fluorocarbon membranes
US3708324A (en) Method of growing silicone elastomer
US4833172A (en) Stretched microporous material
US6235377B1 (en) Microporous membrane with a stratified pore structure created in situ and process
US5885494A (en) Method of forming foamed fluoropolymer composites
US4957787A (en) Artificial flower
US3391221A (en) Fluorocarbon polymer molding compositions
US5908878A (en) High consistency platinum cure elastomer having improved physical properties for fluid handling applications
US2710290A (en) Organopolysiloxane-polytetrafluoroethylene mixtures
US5846604A (en) Controlling the porosity and permeation of a web
US6291563B1 (en) Elastomer dispersion having a unique particle size distribution
US4753978A (en) Curable organosiloxane compositions
US4096227A (en) Process for producing filled porous PTFE products
US5998542A (en) Processing of an elastomer dispersion
US2708289A (en) Method of preparing pressure sensitive organosiloxane sheet material
US6071602A (en) Controlling the porosity and permeation of a web
US2644802A (en) Tetrafluoroethylene polymer compositions containing polyorganosiloxane lubricants
US2938009A (en) Process of treating silica with a siloxane and product thereof
US4649005A (en) Method for producing a liquid silicone rubber base
US3865897A (en) Method of blending polyolefins and polydiorganosiloxane gums and blends thereof
US4472556A (en) Method for enhancing one or more mechanical properties of partially crystalline thermoplastics
US4500659A (en) Extrudable, curable polyorganosiloxane compositions

Legal Events

Date Code Title Description
AS Assignment

Owner name: TETRATEC CORPORATION, 1731 LORETTA AVENUE, FEASTER

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DILLON, JOSEPH A.;DILLON, MARK E.;REEL/FRAME:004655/0779

Effective date: 19861222

Owner name: TETRATEC CORPORATION, A PA PA. CORP.,PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DILLON, JOSEPH A.;DILLON, MARK E.;REEL/FRAME:004655/0779

Effective date: 19861222

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: DONALDSON COMPANY, INC., MINNESOTA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TETRATEC CORPORATION;REEL/FRAME:007945/0782

Effective date: 19940614

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
SULP Surcharge for late payment

Year of fee payment: 11

FPAY Fee payment

Year of fee payment: 12